Crystalline pure 2,4,6-tri-isobutyl dihydro-1,3,5-dithiazine

ABSTRACT

A small but effective amount of a pure crystalline or substantially pure compound represented by the formula: ##STR1## is used to alter, modify or enhance the flavor and aroma characteristics of a foodstuff having a bacon, caramel, roasted meat, roasted nut or fowl flavor and aroma.

This application is a continuation-in-part of application for U.S.letters Pat., Ser. No. 961,684 filed on Nov. 17, 1978.

BACKGROUND OF THE INVENTION

This invention pertains to the use of a certain dithiazine to alter,modify or enhance the flavor and aroma of a foodstuff having a bacon orcaramel or roasted meat or roasted nut or fowl flavor and aroma.

There is a continuing search for compositions which can vary, fortify,modify, enhance or otherwise improve (i.e., alter) the flavor and aromaof a foodstuff. To be fully satisfactory, such compositions should bestable, non-toxic and blendable with other ingredients to provide theirown unique flavor and aroma nuance without detracting from theco-ingredients. Preferably, such compositions should be naturallyoccurring or present in natural foodstuffs (although unrecognized asflavor components thereof) so that their ingestible safety can bereadily recognized. Additionally, these materials should be capable ofbeing synthesized in a simple and economic manner.

Ingredients for foodstuff flavors having aromas and tastes which arecompatible from an esthetic standpoint and from a chemical standpointwith meats and meat flavors are particularly desirable. Morespecifically, roasted, fried and fried bacon and caramel-like (withroasted and burnt nuances) aroma and flavor characteristics areparticularly useful for bacon flavors and caramel flavors. In addition,they are useful for roasted meat, roasted nut and fowl (e.g., chickenand duck) foodstuff flavors and to augment and enhance such flavors.

U.S. Pat. No. 3,966,988 discloses the use of a small but effectiveamount of a compound represented by the formula: ##STR2## wherein R₁, R₃and R₅ are the same and are lower alkyl of from 1 to 5 carbon atoms, R₂,R₄, and R₆ are hydrogen and R₇ is hydrogen or lower alkyl of from 1 to 5carbon atoms; is used to alter, modify or enhance the flavor and aromacharacteristics of foodstuffs, perfumes and perfumed articles.Specifically disclosed and exemplified is the compound2,4,6-trimethyldihydro-1,3,5-dithiazine. This compound is alsospecifically characterized. In addition, however, the compound2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine is disclosed but is notspecifically characterized in said U.S. Pat. No. 3,966,988. Nor is thepure crystalline form of said 2,4,6-tri-isobutyldihydro-1,3,5-dithiazinedisclosed therein.

A bacon flavor is indicated to be prepared according to U.S. Pat. No.3,650,771 issued on Mar. 21, 1972. In said U.S. Pat. No. 3,650,771 thereaction product of 2-aminoethanol hydrosulfide and isovaleraldehyde isindicated to give a strong crisp bacon product when said 2-aminoethanolhydrosulfide and isovaleraldehyde are mixed together and heated over atemperature of 70°-80° C. for a period of about five minutes. It isnoteworthy that the bacon flavor and aroma of the compound having thestructure: ##STR3## is surprisingly intense and longer lasting than isthe bacon flavor and aroma of any of the reaction products of U.S. Pat.No. 3,650,771, particularly the reaction product of 2-aminoethanolhydrosulfide and isovaleraldehyde. On the other hand, the compoundhaving the structure: ##STR4## can be either (i) extracted by means ofhigh pressure liquid chromatography or (ii) isolated by means ofacidification followed by crystallization, neutralization andrecrystallization from the reaction mixture resulting from the reactionof ammonium hydrosulfide with isovaleraldehyde or resulting from thereaction of the shiff base of ammonia and isovaleraldehyde with hydrogensulfide or resulting from the reaction of ammonium sulfide withisovaleraldehyde in the presence of citric acid and water.

The compound having the structure: ##STR5## is specifically disclosed byBeilstein at Vol. I-V-27 (4) wherein it is indicated to have the commonname "Valeraldin" and can be synthesized by reacting ammonia withthioisovaleraldehyde.

No mention is made in any of the prior art including the Beilsteinreference and U.S. Pat. No. 3,966,988 issued on June 29, 1976 of theexistence of pure crystalline or substantially pure2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine or the use thereof as abacon flavor ingredient or a caramel flavor ingredient for itsenhancement, imparting or augmenting properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile of the reaction product produced according toExample I wherein isovaleraldehyde and ammonia is reacted in thepresence of hydrogen sulfide.

FIG. 2 is the GLC profile of the reaction product produced according toExample I, purified by high pressure liquid chromatography (GLCconditions: Carbowax 20 m column; stainless steel 10'×1/8" programmed at65°-210° C. at 15° C. per minute.

FIG. 3 is the NMR spectrum for fractions 17 and 18 resulting from thehigh pressure liquid chromatography separation of the reaction productof Example I. It is pure crystalline or substantially pure2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine.

FIG. 4 is the infrared spectrum for fractions 17 and 18 of the highpressure liquid chromatographic separation product of Example I,crystalline 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine.

THE INVENTION

This invention has to do with the use of pure crystalline orsubstantially pure 2,4,6-tri-isobutyldihydro-1,3,5-dithiazine to alter,modify, enhance the flavor and aroma of a foodstuff having a baconflavor or impart a bacon flavor to a foodstuff.

The pure crystalline or substantially pure2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine of our invention has astructure: ##STR6## and has roasted, fried and fried bacon and aroma andflavor characteristics and in addition a roasted potato skin flavorcharacteristic causing it to be useful in roasted meat, roasted nut,bacon, caramel and fowl flavors. A physical form of2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine, being in pure andcrystalline or substantially pure form is novel per se. The process forpreparing same is also novel in that, heretofore, (i) high pressureliquid chromatographic techniques and (ii) acidification,crystallization, neutralization and recrystallization techniques havenever been used to obtain such a compound from a reaction product.

The 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine of our invention in purecrystalline or substantially pure form is obtained by:

(A) First reacting isovaleraldehyde with ammonia to form a Shiff Baseand reacting the resulting Shiff Base with hydrogen sulfide. Thereaction of the isovaleraldehyde with ammonia takes place at atemperature of between -15° and 0° C. It is preferred that the moleratio of ammonia:isovaleraldehyde is between 2:1 and 1:0.5 with apreferred mole ratio of 1:1.5. The resulting Shiff Base is then reactedwith hydrogen sulfide at atmospheric pressure, preferably at roomtemperature over a period of time of between 1 and 5 hours, preferably2-3 hours. Higher pressures may be used without detrimentally affectingthe yield but no particular advantages are obtained in using pressuresabove one atmosphere.

The reaction product is then extracted with an inert organic solventsuch as anhydrous diethyl ether, the extract is then dried over suchmaterials as anhydrous sodium sulfate and the solvent is stripped off bysuch means as evaporation on a rotary evaporator. The resulting crudematerial is then microdistilled in order to get rid of low boilingfractions and the residue is subjected to column chromatography usingsuch eluting materials as isopentane and/or diethyl ether in isopentanein various percentages of diethyl ether in isopentane such as 0.5% and1%. The resulting fractions from the first column chromatographicseparation are subjected to column chromatography a second time usingfor example a silica column using as eluting agents isopentane, 0.5%diethyl ether in isopentane, 1% diethyl ether in isopentane and 2%diethyl ether in isopentane. A product resulting from the second columnchromatographic separation (combined fractions) are then subjected tohigh pressure liquid chromatography at a rate of between 100 and 500 mlper minute, preferably at about 350 ml per minute. The fractions areanalyzed and selected for the purity of2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in said fractions. In onesuch Example, fractions 17 and 18 were selected yielding 100%2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in crystalline form aftersolvent evaporation.

(B) Reacting isovaleric aldehyde with ammonium sulfide in citric acid inaqueous media at a temperature of between 0° and 15° C. It is preferredthat the mole ratio of ammonium sulfide:isovaleraldehyde is between 2:1and 1:0.5 with a preferred mole ratio of 1:1.5. The reaction time ispreferably between 1 and 5 hours. Higher pressures may be used withoutdetrimentally affecting the yield but no particular advantages areobtained in using pressures above one atmosphere. The resulting reactionmass exists in the form of a "gel" and this "gel" is converted to a two(liquid phase) system--an organic phase and an aqueous phase. Theorganic phase is admixed with aqueous mineral acid, for example, 5%hydrochloric acid whereupon a crystalline precipitate is formed. Thecrystals are separated and washed with a non-dissolving hydrocarbon,such as hexanes and then neutralized by dissolving in a solvent, such asdiethyl ether and treating with a weak base, such as 5% aqueous sodiumcarbonate. The excess base is then washed out and the organic solutionis dried and evaporated yielding the pure or substantially pure2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in crystalline form.

The structural formula for 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazinegiven herein contemplated and includes cis and trans and otherconformational isomers. When the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure and crystalline orsubstantially pure form according to this invention is used in aflavoring composition, it can be combined with conventional flavoringmaterials or adjuvants. Such co-ingredients or flavoring adjuvants arewell known in the art for such use and have been extensively describedin the literature. Apart from the requirement that any such adjuvantmaterial be ingestibly acceptable, and thus non-toxic or otherwisenon-deleterious conventional materials can be used and broadly includeother flavor materials, vehicles, stabilizers, thickeners, surfaceactive agents, conditioners and flavor intensifiers.

The term "foodstuff" as used herein includes both solid and liquidingestible materials for man or animals which materials usually do, butneed not, have nutritional value. Thus, foodstuffs include meats,gravies, soups, convenience foods, malt and other alcoholic ornon-alcoholic beverages, nut butters such as peanut butter and otherspreads, seafoods including fish, crustaceans, mollusks and the like,candies, breakfast foods, baked goods, vegetables, cereals, soft drinks,snack foods, pet foods such as dog and cat foods, other veterinaryproducts, and the like.

The terms "alter" and "modify" (in their application to foodstuffs) inits various forms will be understood herein to mean the supplying orimparting of a flavor character to note to an otherwise bland,relatively tasteless substance, or augmenting and existing flavorcharacteristic where the natural flavor is deficient in some regard, orsupplementing the existing flavor impression to modify the organolepticcharacter.

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

Conventional flavoring materials as indicated above include saturatedand unsaturated fatty and amino acids, alcohols, including primary andsecondary alcohols; esters, carbonyl compounds including ketones andaldehydes; lactones, other cyclic organic materials including benzenederivatives, alicyclics, hetero-cyclics such as furans, pyridines,pyrazines and the like; sulfur-containing materials including thiols,sulfides, disulfides and the like; proteins; lipids; carbohydrates;so-called flavor potentiators such as monosodium glutamate, guanylates,and inosinates; natural flavoring materials such as cocoa, vanilla andcaramel; essential oils and extracts such as anise oil, clove oil andthe like; artificial flavoring materials such as vanillin; and the like.Particularly useful flavoring agents and adjuvants are cyclopentanethiol, protein hydrolysate, such as hydrolyzed vegetable protein,cysteine, salts of cysteine such as cysteine hydrochloride, thiamine,salts of thiamine, 2,5-dimethyl-3-hydroxy-4-oxo-4,5-dihydrofuran, andproducts resulting from heating a mixture of at least two differingmaterials of the foregoing and high pressure (2-10 atmospheres) reactionproducts of H₂ S and 2,5-dimethyl-3-hydroxy-4-oxo-4,5-dehydrofuran,heliotropin, cyclotene, ethyl cyclotene, maltol, ethyl maltol, 6-methylcoumarin, vanillin, ethyl vanillin, levulinic acid, isovaleraldehyde,furfural, rum ether, ethyl levulinate and peruvic acid.

Stabilizers include preservatives such as sodium chloride, and the like;antioxidants such as calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate andthe like; sequestrants such as citric acid, EDTA, phosphates, and thelike.

Thickeners include carriers, binders, protective colloids, suspendingagents, emulsifiers and the like, such as agar-agar, carrageenan,cellulose and cellulose derivatives such as carboxymethyl cellulose andmethyl cellulose, natural and synthetic gums such as gum arabic, gumtragacanth and the like, and other proteinaceous materials, lipids,carbohydrates, starches and pectins.

Surface active agents include emulsifying agents such as mono-and/ordiglycerides of fatty acids such as caproic acid, caprylic acid,palmitic acid, myristic acid, oleic acid, and the like; lecithin;defoaming and flavor-dispersing agents such as sorbitan monostearate,potassium stearate, hydrogenated tallow alcohol, and the like.

Conditioners include compounds such as bleaching and maturing agentssuch as benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like; buffersand neutralizing agents such as sodium acetate, sodium diacid phosphate,ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid,vinegar and the like; colorants such as carminic acid, cochineal,turmeric, curcumin, approved food and drug dyes, and the like; firmingagents such as aluminum sodium sulfate, calcium chloride and calciumgluconate; texturizers; anti-caking agents such as aluminum calciumsulfate and tribasic calcium phosphate; enzymes, yeast foods such ascalcium lactate and calcium sulfate; nutrient supplements such as ironsalts, such as ferric phosphate, ferric pyrophosphate, ferrous gluconateand the like, riboflavin, vitamins; zinc sources such as zinc chloride,zinc sulfate and the like.

The 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form, or the compositions incorporating them, asmentioned above, can be combined with one or more vehicles or carriersfor adding them to the particular product. Vehicles can be edible orotherwise suitable materials such as ethyl alcohol, propylene glycol,water, and the like. Carriers include materials such as gum arabic,carrageenan, other gums, and the like. The2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form can be incorporated with the carriers byconventional means such as spray-drying drum drying, and the like. Suchcarriers can also include materials for coacervating the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form (and other flavoring ingredients, as present) toprovide encapsulated products. When the carrier is an emulsion, theflavoring composition can also contain emulsifiers such as mono- anddiglycerides of fatty acids and the like. With these carriers orvehicles, the desired physical form of the composition can be prepared.

It will be understood by those skilled in the art that the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form can be added to the materials to be flavored atany convenient point in the production of the finished product. Thus,when they are used to alter or otherwise vary the flavor of a foodstuff,they can be added in the original mixture, dough, emulsion, batter orthe like, prior to any cooking or heating operation. Alternatively, theycan be added at a later state of processing if volatilization losseswould be excessive during the earlier processing.

The quantity of 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in purecrystalline or substantially pure form or mixtures thereof utilizedshould be sufficient to impart the desired flavor characteristic to theproduct, but on the other hand, the use of an excessive amount of the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form is not only wasteful and uneconomical but insome instances too large a quantity may unbalance the flavor or otherorganoleptic property of the product to be consumed. The quantity usedwill vary depending upon the ultimate foodstuff or other consumableproduct; the amount and type of flavor initially present in the product;the further process or treatment steps to which the product will besubjected; regional and other preference factors; the types of storage,if any, to which the product will be subjected; and the preconsumptiontreatment, such as baking, frying, and so on, given to the product bythe ultimate consumer.

It is accordingly preferred that the ultimate compositions contain fromabout 0.002 parts per million (ppm) to about 100 ppm of the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form. More particularly, in food compositions it isdesirable to use from about 0.02 to about 20 ppm and in certainpreferred embodiments of the invention, from about 0.1 to about 15 ppmof the 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystallineor substantially pure form are included in the finished product.

The amount of 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in purecrystalline or substantially pure form to be utilized in flavoring orflavor-enhancing compositions can be varied over a wide range dependingupon a particular quality to be added to the foodstuff, tobacco, orother consumable material. Thus, amounts of one or more2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystalline orsubstantially pure form according to the present invention from about0.02 up to 80 or 90% can be incorporated in such compositions. It isgenerally found to be desirable to include from about 0.02 to about 25%of the 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine in pure crystallineor substantially pure form in such compositions.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

All parts, proportions, percentages, and ratios herein are by weightunless otherwise indicated.

EXAMPLE I PREPARATION OF PURE CRYSTALLING OR SUBSTANTIALLY PURE2,4,6-TRI-ISOBUTYL-DIHYDRO-1,3,5-DITHIAZINE Reaction: ##STR7##

Into a 1 liter, 3-neck flask equipped with mechanical stirrer,additional funnel, thermometer and condenser is placed 350 grams of 30%aqueous ammonia with stirring at -9° C. 172 Grams of isovaleraldehyde isadded dropwise over a 45 minute period while maintaining the reactiontemperature at between -10° C. and 0° C.

The addition funnel is then removed and the solids on the inside glasswall of the flask are washed with 150 ml water. The flask is thenstoppered. The reaction mass is then allowed to come to room temperaturewith stirring over a period of 130 minutes.

The flask is unstopped and hydrogen sulfide gas is bubbled into thereaction mass over a period of 1 hour and 45 minutes via a gasdispersion tube.

Three hundred ml volumes of diethyl ether is then used to extract theorganic layer. The ether layer is then washed with saturated sodiumchloride-water until neutral and dried over anhydrous sodium sulfate.The solvent is then removed by means of a rotary evaporator and 150grams crude material is obtained.

A sample of the crude material is trapped out using GLC trapping(conditions: SE 30 stainless steel 10'×1/8" column programmed at65°-210° C. at 6° C. per minute.

GLC profile is set forth in FIG. 1.

In order to remove the "lights" the material is microdistilled under 0.5mm Hg pressure. The distillation is continued and the temperature in thedistillation flask reaches 120° C. The residue in the distillation flaskis removed and subjected to column chromatography on a 5% H₂ Odeactivated SiO₂ column (850 grams). Thus, 35 grams of crude materialfrom the distillation flask is placed on the column using the followingsolvents:

a. 4 liters isopentane

b. 4 liters 0.5% diethyl ether in isopentane

c. 8 liters 1% diethyl ether in isopentane

The fractions are monitored using thin layer chromatography and gaschromatography. The combined fractions indicate 90% purity on GLC. Thecombined fractions weights about 10 grams.

The resulting combined material is again subjected to a second columnchromatographic separation using undeactivated SiO₂, 200 grams. 9 Gramsof the first combined column chromatography-separated material issubjected to the column and the solvents used are as follows:

a. 1 liter isopentane

b. 0.6 liters 0.5% diethyl ether in isopentane

c. 1.5 liters 1% diethyl ether in isopentane

d. 1.5 liters 2% diethyl ether in isopentane

The fractions are combined and indicate 92% pureity. The weight of theresulting material is 8.5 grams.

About 4 grams of this material obtained from the second columnchromatographic separation is injected on a "Ater's" preparatory "500"high pressure liquid chromatography column. The fractions collected aremonitored by thin layer chromatography. The "best" fractions observed onthin layer chromatography indicate 98% purity on GC. The high pressureliquid chromatography GC profile is set forth in FIG. 2.

The high pressure liquid chromatography conditions are:

350 ml/minute: one SiO₂ column chart speed

0.5 inches per minute.

The material obtained from high pressure liquid chromatography is about2.3 grams. Fractions 17 and 18 are combined. The fractions 17 and 18 are100% 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine having the structure:##STR8##

The NMR spectrum for fractions 17 and 18 of the high pressure liquidchromatography separation is set forth in FIG. 3. The IR analysis forfractions 17 and 18 resulting from the high pressure liquidchromatography separation is set forth in FIG. 4.

The GC conditions for the GC profile of the high pressure liquidchromatography separation product are:

Carbowax 20 m column: stainless steel 10'×1/8" programmed at 65°-210° C.at 15° C. per minute.

The Mass Spectral analysis for the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine, crystallized and purifiedof fractions 17 and 18 is as follows:

    ______________________________________                                        M/E           Relative Intensity                                              ______________________________________                                        39            29                                                              41             79.sup.2                                                       43            100.sup.1                                                       45             37.sup.6                                                       58            36                                                              60             40.sup.5                                                       69             50.sup.4                                                       87            35                                                              96            30                                                              102            54.sup.3                                                       M289           5                                                              ______________________________________                                    

EXAMPLE II

The following ingredients are homogeneously admixed at 25° C:

    ______________________________________                                        Ingredients           Parts                                                   ______________________________________                                        Vegetable Shortening  622.7                                                   Salt                  321.7                                                   Glutamic Acid         5.1                                                     L-Cysteine Hydrochloride                                                                            10.3                                                    Glycine               5.1                                                     β-Alanine        1.3                                                     Taurine               20.0                                                    Mixture of di-sodium  3.3                                                     inosinate and di-sodium                                                       guranylate                                                                    ______________________________________                                    

The mixture is heated to 300° F. for 30 seconds. After cooling to 100°F., 0.05 parts of 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine,crystallized and purified or substantially purified produced accordingto Example I are added.

The resulting mixture has an excellent bacon aroma and taste.

EXAMPLE III

Cysteine hydrochloride in the amount of 8.8 g is refluxed at 215° F.under atmospheric pressure for four hours with a mixture of 309 g ofhydrolyzed vegetable protein and 674 g of water. Subsequent to thereflux, the mixture is cooled and 0.05 g of2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine, crystallized and purifiedor substantially purified produced according to Example I is added andintimately admixed with the composition. The mixture has an excellentfried bacon flavor of high intensity.

EXAMPLE IV

The composition prepared in Example II is dissolved in propylene glycolto provide a 0.1% solution. This solution in the amount of 0.966 g isadded to 7.3 g of a soup base consisting of:

    ______________________________________                                        Ingredients           Parts                                                   ______________________________________                                        Fine ground sodium chloride                                                                         35.62                                                   Hydrolyzed vegetable protein                                                                        27.40                                                   Monosodium glutamate  17.81                                                   Sucrose               10.96                                                   Beef fat              5.48                                                    Sethness caramel color                                                                              2.73                                                    (powder B & C)                                                                ______________________________________                                    

The resulting mixture is added to 12 ounces of boiling water to obtain asoup having an excellent bacon flavor.

EXAMPLE V

The composition prepared in Example III is dissolved in propylene glycolto provide a 0.1% solution. This solution in the amount of 0.966 g isadded to 7.3 g of a soup base consisting of:

    ______________________________________                                        Ingredients           Parts                                                   ______________________________________                                        Fine ground sodium chloride                                                                         35.62                                                   Hydrolyzed vegetable protein                                                                        27.40                                                   (Maggi 4BE)                                                                   Monosodium glutamate  17.81                                                   Sucrose               10.96                                                   Beef fat              5.48                                                    Caramel color, bakers and                                                                           2.73                                                    confectioner's powder                                                         grade                                                                         ______________________________________                                    

The resulting mixture is added to 12 ounces of boiling water to obtain asoup having an excellent bacon flavor.

EXAMPLE VI

One-half gram of the soup base mixture of Example IV is emulsified in asolution containing 100 g gum arabic and 300 g water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 250 cfm of air withan inlet temperature of 500° F., an outlet temperature of 200° F., and awheel speed of 50,000 rpm.

Twelve grams of the spray-dried material is mixed with 29.2 g of thesoup base set forth in Example IV. The resulting mixture is then addedto 12 ounces of boiling water and an excellent bacon flavored soup isobtained.

EXAMPLE VII LARGE SCALE PREPARATION OF CRYSTALLINE2,4,6-TRI-ISOBUTYL-DIHYDRO-1,3,5-DITHIAZINE Reaction: ##STR9##

To a 22 liter reaction flask equipped with air stirrer, cooling bath,thermometer, addition funnel, reflux condenser and gas outlet andbubbler, dry trap, 30% caustic trap and nitrogen inlet, 6,480 grams ofdistilled water is added followed by 4,146 grams of citric acid. Theflask is then packed with wet ice and cooled to 10° C. 1,395 Grams ofisovaleric aldehyde is added to the reaction mixture which is againcooled to 10° C. Over a period of 1 hour, 2,502 grams of 22% ammoniumsulfide is added to the reaction mass while maintaining it at atemperature in the range of 10°-18° C. and applying a nitrogen sweep tothe head space in the reaction flask. The reaction mass is then stirredfor a period of 10 hours whereby the gel formed therein is converted tooil.

The reaction mass is poured into a 10 gallon open head funnel and theflask is rinsed with 1 liter of diethyl ether. The ether washings arealso poured into the open head separatory funnel. The contents of theseparatory funnel is stirred slowly for a period of 3 minutes and thenpermitted to separate into two liquid phases. The upper organic layer isremoved and the lower aqueous layer is extracted with two 1 litervolumes of diethyl ether. The organic phase and the ether extracts arecombined with the reaction product resulting from a second run identicalto the first run above.

Into a 12 liter separatory funnel the filtered organic layers from thetwo runs are added together with 2 liters of a 5% hydrochloric acidsolution. The contents of the separatory funnel are stirred andpermitted to separate. A white salt forms. The aqueous layer is removedand discarded and the solids are filtered from the organic layer. Thecrystals are washed with portions of diethyl ether totaling 600 mlyielding 920 grams of salt. To the filtrate, 1.4 liters of 5%hydrochloric acid solution is added with stirring. More white crystalsare formed and permitted to separate. The lower aqueous layer isdiscarded and the organic layer is filtered and the crystals are washedwith anotheer 600 ml of diethyl ether. To the filtrate, another 1.4liters of 5% hydrochloric acid solution is added with stirring and asmaller amount of white crystals is formed and permitted to separate.Again, the lower aqueous layer is discarded. The upper organic layer isfiltered and the crystals are washed with 600 ml ether. All crystalbatches are combined for washing (1025 grams wet weight).

The resulting combined solids are slurried in a 5 liter flask with 3,000ml hexane. The material is then filtered and the filter cake is rinsedwith portions of hexane totaling about 1.5 liters. GLC analysis at thispoint indicates all trimer of isovaleric aldehyde (by product) iseliminated.

The solids are added to a 20 liter separatory funnel followed by 6liters of diethyl ether and 5 liters of a 5% aqueous sodium carbonatesolution. The contents of the separatory funnel are then stirredvigorously until they dissolve. The upper ether layer is removed and thelower aqueous layer is extracted with two 1 liter volumes of diethylether. The organic phases are combined and washed with 1 liter ofsaturated sodium chloride until the pH is between 6 and 7. The organiclayer is then dried over 260 grams of anhydrous magnesium sulfate. Theresulting dried material is distilled using a 3 liter distillation flaskand a "continuous feed rush over apparatus". The product remaining inthe distillation flask is filtered and rinsed with cold diethyl ether(400 ml). The resulting crystals are dried yielding 160 grams ofproduct. Recrystallizations are carried out from the mother liquoryielding a total of 450 grams of the product.

GLC, NMR and IR analyses yield the information that this product issubstantially pure 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine havingthe structure: ##STR10##

EXAMPLE VIII BASIC BACON FLAVOR FORMULATION

The following basic bacon flavor formulation is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Vanillin              2.0                                                     Eugenol               1.0                                                     Guaicol               0.2                                                     Para-vinyl guaicol    0.2                                                     Cyclotene             1.0                                                     Trimethyl pyrazine    0.4                                                     Acetyl pyridine       0.1                                                     2,4-Decadienal (1% in food grade                                                                    0.1                                                     ethanol)                                                                      Furfural              0.4                                                     Benzaldehyde          1.0                                                     Isovaleraldehyde      1.0                                                     Methyl thiazole alcohol                                                                             7.6                                                     Food grade Ethanol    185.0                                                   Hickory Smoke Flavor                                                          (obtained from        800.0                                                   Fleischmann Distilling                                                        Corporation, Inc.,                                                            625 Madison Avenue,                                                           New York, New York)                                                           ______________________________________                                    

The above formulation is divided into parts. To the first part, nothingis added. To a second part at the rate of 0.02 ppm, the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine produced according toExample VII is added. Both basic bacon flavor formulations with andwithout the dithiazine prepared according to Example VII are compared atthe rate of 100 ppm and evaluated by a flavorist expert panel. Theflavor with the 2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine producedaccording to Example VII has a crisp bacon aroma and taste andadditional pork fat notes not present in the basic bacon flavor.Therefore, the flavor with the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine is preferred by the panel.

EXAMPLE IX BASIC CARAMEL FLAVOR FORMULATION

The following basic caramel flavor formulation is prepared:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        Heliotropine       1.0                                                        Cyclotene          2.0                                                        Maltol             3.0                                                        6-Methyl-coumarin  3.0                                                        Vanillin           4.0                                                        Ethyl vanillin     3.0                                                        Levulinic acid     8.0                                                        Isovaleraldehyde   0.5                                                        Furfural           0.1                                                        Rum Ether          20.0                                                       Ethyl Levulinate   0.9                                                        Pyruvic Acid       15.0                                                       ______________________________________                                    

This basic caramel flavor formulation is divided into two portions. Tothe first portion, nothing is added. To the second portion at the rateof 0.01 ppm, 2,4,6-tri-isobuyl-dihydro-1,3,5-dithiazine preparedaccording to Example VII is added. The flavor with and without said2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine are compared at the rate of10 ppm in water by a flavorist panel. The flavor with the2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine has a very characteristicroasted and burnt character in both aroma and taste; not nearly as muchas exists in the flavor without said dithiazine. Therefore, the flavorwith the additional note is preferred by the bench panel of flavorists.

What is claimed is:
 1. Pure crystalline2,4,6-tri-isobutyl-dihydro-1,3,5-dithiazine having the structure:##STR11##